accutof gcv 4g - jeol usa...there is no need to break vacuum when you switch ion modes. it is ... fd...
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JEOL
“AccuTOF GCv 4G“ : Petroleum Sample Analysis with EI/FI/FD combination ion source and Applications.
JEOL USA, Inc.
JEOL
Topics
1. Instrument
2. Samples and Measurement conditions
3. TIC chromatogram
4. Mass spectra of EI and FI
5. Conclusion
6. Examples of other hydrocarbon
applications
2
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1. Instrument
• JMS-T100GCV “AccuTOF GCv 4G” basic unit • Resolving power: R≥8,000 (FWHM) @ m/z 617
• Mass range: m/z 4-5000
• Mass accuracy: 1.5 mDa or 4 ppm (RMS)
• Sensitivity: S/N ≥ 100 for 1pg OFN (using with EI standard ion source)
• Acquisition rate: 50 spectra/s
• Auto Tuning for all ionization modes
• “EI/FI/FD Combination Ion Source” option • EI, FI and FD modes can be switched without breaking vacuum
• Suitable for petroleum analysis
• Additional options • CI mode (Positive and Negative)
• Direct insertion: DEP, DIP, FD, LIFDI*
Liquid Injection Field Desorption Ionization:
Allows continuous sample introduction onto the FD emitter without removing the probe.
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1. EI/FI/FD Combination Ion Source
EI, FI and FD modes can be switched without breaking vacuum
Cathode for FI/FD
Filament for EI
Lens unit
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2. Samples and Measurement Conditions
• Sample: • Diesel oil
• Measurement conditions: • Column: DB-5ms, 30 m x 0.25 mm, 0.25 um
• Oven: 50 C(1min) → 20 C/min → 300 C(6.5 min)
• Inlet: 300 C, Split 200:1, 0.2 uL inj.
• EI: 70 eV, 300 uA
• FI: -10 kV (Cathode), 45 mA (30 msec: Refreshed every spectra
recording
• Mass range: m/z 35-800
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3. TIC Chromatograms TIC[1]; / EI+(eiFi) / EI+(eifi)_DieselOil_1023_003 0.2uL Inj, Split200
0
2
4
6
8
10
12
14
16
Intensity (17885739)x106
9.819.22
8.61 10.89
4.907.96 11.39
5.74 6.53 7.27
11.87
9.50
4.01 12.339.00
8.357.53
12.766.23 7.065.38 11.114.59 13.19
TIC[1]; / FI+(eiFi) / FI+(eifi)_DieselOil_1024_002 0.2uL Inj, Split200
2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0Time[min]
0
500
1000
1500
2000
2500
Intensity (2515297)x103
9.23 9.81 10.37
8.61
11.39
7.96
11.87
7.27
6.5312.33
5.75 9.014.9012.778.36
GC/EI
GC/FI
C11H24 C12H26 C13H28
C14H30
C15H32
C16H34
C17H36
C18H38
C19H40
C20H42
C21H44
C22H46
C23H48
C10H22
+
C9H12
C24H50
C25H52
C26H54
C9H20
C9H20
C10H22
+
C9H12 C11H24
C12H26
C13H28
C14H30
C15H32
C16H34 C17H36 C18H38
C19H40
C20H42
C21H44
C22H46
C24H50
C25H52
C23H48 C26H54
m/z 207.0329 (Background)
is used as external calibrant
m/z 226.26605 (C16H34)
is used as external calibrant
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4. Mass spectra of the component at R.T. 4.90 MS[1];4.89..4.91;-1.0*MS[1];4.93..4.94; / EI+(eiFi) / EI+(eif i)_DieselOil_1023_003
0.2uL Inj, Split200
0
50
100
150
200
Intensity (244804)x103
57.07143.055
105.070
71.085
85.100
120.093
56.062
70.07755.054
84.093
119.085142.17299.11691.054
58.07351.023
MS[1];4.89..4.91; / FI+(eiFi) / FI+(eif i)_DieselOil_1024_002
0.2uL Inj, Split200
40 60 80 100 120 140 160 180 200
m/z
0
5
10
15
20
25
Intensity (27559)x103
142.172
120.095
143.176
121.100
EI
FI
M+・, C10H22
(0.8 mDa)
M+・, C9H12
(1.6 mDa)
M+・, C10H22
(-0.2 mDa)
M+・, C9H12
(-0.7 mDa)
C8H9
(-0.4 mDa)
C6H13
(-1.0 mDa)
C5H11
(-0.8 mDa)
C4H9
(0.9 mDa) C3H7
(0.6 mDa)
No fragment ions
FI spectrum showed that
the component at R.T. 4.90 (min)
consists of different two
hydrocarbons.
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Mass Spectra of n - Paraffins 1
EI FI
C11H24
C12H26
C13H28
C9H20
C11H24
C12H26
C13H28
C9H20
M+・ (0.6 mDa)
M+・ (0.8 mDa)
M+・ (1.1 mDa)
M+・ (-0.7 mDa)
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Mass Spectra of n - Paraffins 2
EI FI
C15H32
C16H34
C17H36
C14H30
C15H32
C16H34
C17H36
C14H30
M+・ (1.2 mDa)
M+・ (-0.1 mDa)
m/z 226.26605
is used as
external
calibration
M+・ (1.0 mDa)
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Mass Spectra of n - Paraffins 3
EI FI
C19H40
C20H42
C21H44
C18H38
C19H40
C20H42
C21H44
C18H38
M+・ (-0.9 mDa)
M+・ (-0.6 mDa)
M+・ (-0.9 mDa)
M+・ (-2.2 mDa)
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Mass Spectra of n - Paraffins 4
EI FI
C23H48
C24H50
C25H52
C22H46
C23H48
C24H50
C25H52
C22H46
M+・ (-2.4 mDa)
M+・ (-1.5 mDa)
M+・ (-0.5 mDa)
M+・ (-2.9 mDa)
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MS[1];3.35..14.33; / FI+(eiFi) / FI+(eif i)_DieselOil_1024_002-Centroided
0.2uL Inj, Split200
100 200 300 400 500 600 700 800
m/z
0
500
1000
1500
Intensity (1835)
226.270 240.285
212.252 268.313
174.143282.327
160.127
43.053296.340
146.111310.357
120.095324.372
MS[1];1.32..14.80;-1*MS[1];16.21..17.98; / EI+(eiFi) / EI+(eif i)_DieselOil_1023_003-Centroided
0.2uL Inj, Split200
100 200 300 400 500 600 700 800
m/z
0
10
20
30
40
50
Intensity (54244)x103
57.070
71.085
85.101
97.100
133.100
165.070
Sum Over the Entire R.T. Range
EI
FI FI is well suited for petroleum analysis because it is
the only soft ionization method that works well for
saturated hydrocarbons.
We can detect molecular ions for hydrocarbons with
FI and calculate molecular weight distributions.
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5. Conclusion
• The AccuTOF GCv has a unique EI/FI/FD combination ion source.
There is no need to break vacuum when you switch ion modes. It is
only necessary to replace the EI repeller probe with the FI/FD
emitter probe without breaking vacuum.
• FI method is well suited for petroleum analysis, because it can
generates molecular ions for saturated hydrocarbons with minimal
fragmentation.
• EI and FI mass spectra both showed excellent mass accuracy.
• The AccuTOF GCv can be used for GCxGC measurement. We have
also demonstrated applications for GCxGC/FI with high-resolution
mass spectra.
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6. Other Hydrocarbon Applications
• Commercial Lubricants Analysis with GC/FI
• Crude Oil Measurement with GC/FI
• Type Analysis of Crude Oil using a FI Mass Spectrum
• Microcrystalline Wax measurement with FD
• Rapid analysis using inactivated fused silica tube as a sample inlet
• GC x GC/EI - Dibenzothiophenes analysis in Kerosene
• GC x GC/FI technique with normal and reverse column set
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Commercial Lubricants Analysis with GC/FI
C13H28 (M+・: m/z 184.2191, external calibrant)
*
Hydrocarbons Fatty acid esters
A B
C
D
min
Formula Calc. m/z Meas. m/z Mass error (mDa)
A C11H24 156.1878 156.1868 -1.0
B C12H26 170.2034 170.2030 -0.4
C C20H40O2 312.3028 312.3046 1.8
D C22H44O2 340.3341 340.3356 1.5
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Crude Oil Measurement with GC/FI
TIC Chromatogram
FI Mass Spectrum
Accumulation over entire time range
Hydrocarbons could be detected as molecular ions
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Type Analysis of Crude Oil by using an FI Mass Spectrum
* Polymerix software (Sierra Analytics, Inc.)
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Microcrystalline Wax measurement with FD
FD Mass Spectrum
Mn Mw Mz PD DPn DPw DPzPercetSeries
PercentSpectrum
657.0 686.9 718.9 1.0 40.1 42.2 44.5 100.0 64.1
S1 CnH2n+2 571.1 617.3 665.3 1.1 33.6 36.9 40.3 17.3 11.1
S2 CnH2n 529.7 655.0 680.8 1.0 37.9 39.7 41.6 24.2 15.5
S3 CnH2n-2 670.5 692.3 715.6 1.0 41.0 42.5 44.2 13.1 8.4
S4 CnH2n-4 715.6 739.0 764.7 1.0 44.3 46.0 47.8 8.4 5.4
S5 CnH2n-6 688.3 717.9 751.1 1.0 42.5 44.7 47.0 22.5 14.5
S6 CnH2n-8 710.0 739.6 772.8 1.0 44.2 46.3 48.7 14.5 9.3
SeriesLabel
Total/Average
Type Analysis of Microcrystalline Wax
Mn:Number-average M.W. Mw:Weight-average M.W. Mz:Z-average M.W. PD:Mw/Mn DPn: Mn/R DPw: Mw/R DPz: Mz/R (R: Repeating unit)
FD type analysis can provide information such as component ratios and average molecular weight.
Unsaturated hydrocarbons Saturated
hydrocarbons
300 400 500 600 700 800 900 1000 1100 1200 1300 m/z
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Rapid analysis using inactivated fused silica tube (a.k.a. “guard column”) as a sample inlet
MS
GC Oven (prog.)
Inlet
GC Oven (iso.)
Fused silica tube
Capillary column:
ZB-5ms, 30 m × 0.25 mm, 0.25 µm Fused silica tube: 3 m ×0.1 mm
Capillary column
MS
Inlet(a) (b)
Rela
tive
inte
nsi
ty /
%R
ela
tive
inte
nsi
ty /
%R
ela
tive
inte
nsi
ty /
%
m/z
m/z
m/z
Rela
tive
inte
nsi
ty /
%R
ela
tive
inte
nsi
ty /
%R
ela
tive
inte
nsi
ty /
%
m/z
m/z
m/z
Time / min
Time / min
Time / min
(A)
(B)
(C)
(a)
(b)
(c)
Fig.2 TICs of diesel oil
(a) blank tube inlet/FI,
(b) capillary GC/FI, (c) FD
Fig.3 Mass spectra of diesel oil
(A) blank tube inlet/FI,
(B) capillary GC/FI, (C) FD
MS
GC Oven (prog.)
Inlet
GC Oven (iso.)
Fused silica tube
Capillary column:
ZB-5ms, 30 m × 0.25 mm, 0.25 µm Fused silica tube: 3 m ×0.1 mm
Capillary column
MS
Inlet(a) (b)
Fig.1 Schematic diagrams of sample
introduction system by using GC,
(a) capillary GC/FI. (b) blank tube inlet/FI.
• Short analysis time
• Loss of low boiling point components are
minimized compared with probe-based
methods, such as FD, DEI, and DCI, in
which the sample is deposited on the probe
at ambient pressure.
• Loss of high boiling point and trace
components is minimized compared to
GC/MS methods since there are no
interaction with a GC stationary phase.
• GC conditions are not critical; no need to
worry about separation parameters.
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GC x GC/EI – Kerosene and Diesel Oil
2-D TIC of
Kerosene (EI)
2-D TIC of
Diesel Oil (EI)
A time-of-flight mass spectrometer (TOFMS) is the best detector for GCxGC
because it is capable of rapid spectral acquisition with no spectral skewing.
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GC x GC/EI - Dibenzothiophenes in Kerosene
A, C12H8S
m/z 184.0343
Error: -0.4 mDa
B, C13H10S
m/z 198.0495
Error: -0.8 mDa
C, C14H12S
m/z 212.0654
Error: -0.6 mDa
TIC 2-D Mass chromatogram
A B C
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GC x GC/FI technique with normal column set
GCxGC condition : 1st column : BPX5, 30mx0.25mm, I.D. 0.25um : 2nd column : BPX50, 2mx0.1mm, I.D. 0.1mm : Oven temp. prog.: 50℃(2min)→3℃/min→300℃
TOFMS condition : Mass range : m/z 35 ~ 500 : Data acquisition speed : 0.04 sec/spectrum : Ionization mode : FI, cathode voltage -10kV
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GC x GC/FI technique with reverse column set
GCxGC condition : 1st column : DB-WAXETR, 30mx0.25mm, I.D. 0.1um : 2nd column : DB-1, 1mx0.1mm, I.D. 0.1um : Oven temp. prog.: 50℃(2min)→3℃/min→300℃
TOFMS condition : Mass range : m/z 35 ~ 500 : Data acquisition speed : 0.04 sec/spectrum : Ionization mode : FI, cathode voltage -10kV
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